Process fob catalytic conversion of



- c This application is Patented Jan. 23,

PROCESS FOR CATALYTIC CONVERSION OF GASEOUS HYDROCARBONS Boris Malishev,

Elizabeth, N. J., assignor of thirty and one-third per cent to UniversalDevelopment Corporation, New York, N. Y., and three per cent to-John P.Nikonow, New York,

No Drawing.

'Application January 24, 1039, Serial seesaw 4 Claims. (Cl. 196-101 Myinvention relates to catalytic reactions of hydrocarbons andhasparticular reference to polymerization of oleiinic gases into liquidhydrocarbons. v

a continuation-impart of my application Serial No. 194,796, filed March9, 1938, which matured into. Patent No. 2,148,634; and Serial No.205,724,-flled May 3, 1938, which matured into Patent. No. 2,148,378.

'10 In the process of cracking hydrocarbon oils such as are used forobtaining'an increased yield oi gasoline and similar --lighthydrocarbons; a more or less large amount of gases, uncondensable atnormal temperature andpressure, are

- 1 formed consisting of hydrogen, saturated hydrocarbons, and, oleiins.These gases containing sometime as much as 50% oleflns cannot be usedeconomically for any practical purposes and are usually largely wasted.To prevent such a waste, methods have been developed iorpolymerlzationoi the oleiinic component of these gases, one of such methods involvingthe use ofa catalyst comprising phosphoric acid .calcined with adsorbentmaterials such as kieselguhr. I .5 have found, however, that aneffective polymerization can be obtained with the use of my catalystrepresenting a calcined mixture of a mineral phosphate or Thomas slag,(including, of course, such modified forms of the mineral phosphates assuper-phosphates, etc.) with sulfuric acid (including sulfuric acidanhydride, sludge acid, etc.) .the calcination being conducted at atemperature sumcient to largely .expel the sulfuric acid but below redheat.

catalyst was-fully. described in my United States patent applicationsSerial Serial No. 140,441,

tiled May 3, 1937; 194,769, filed March 9, 1938; I

and 205,724, flle'd May 3, .1938, this application .being continuationin part of the application No. 140,441. I have found that my catalyst issuitable ior polymerization orsynthesis of hydrocarbons, especiallynormally gaseous oleilneslnto gasoline-like products; for treatingpetroleum and coal tar products} for refining gasoline and ll improvingits anti-knock properties; for alkylating aromatic hydrocarbons witholefines, and for various other purposes when catalytic conversion maybe used.

The oleflnic gases from cracking oils in gaso-.

l line'manufacturecontain a considerable amount of paramn hydrocarbons,which are exceedingly stable and do not react at the temperature atwhich the oleflns are cataiytically polymerized. It is known thatnormally gaseous pa can ll be converted into the more reactive oleflnsby.

v and high copper dish gum was pumped through a bed of my catalyst at225 00,

The preparation of my cracking; but this requires a very hightemperature of about 750 C. and gives a pocr conversion as aconsiderable amount of hydrocarbons is decomposed into carbon. Now Ihave found, that with my catalyst, the parafllnic gases can be 5 crackedat relatively low temperature such as 400-450 C. and converted with agood yield to olefins whereby very little carbon is formed.

1 polymerize by a two step process a mixturev of olefinic and paraiilnicgases such as are obtained from cracking. In the first step, the mixtureof gases is heated over my catalyst at 400-450 C. whereby the parafflnicgases are converted into olefins. In the second step, the obtained,gleflnic product is polymerized with my catalyst to gasoline at atemperature of 200-250 C. and a pressure of between '7 to atmospheres.

Example 1.--A mixture of normally gaseous hydrocarbons, such as isobtained in a cracking process and containing ethylene, propylene, and80 butylene was passed through my catalytic mass downwardly at atemperature of 200 C. and at a pressure of 10 atmospheres. In thismanner about 75% of the oleflnic gases were converted into a gasoline ofgood quality, having an octane number of 82. Example 2.-A crackedunrefined gasoline of yellow color, poor induction period (=2 hours)(600 mg per 100 cc.)

C. and at 200 pounds pressure. ,The product was redistilled to thedesired endpoint. The gasoline thus refined had a Saybolt color of acopper dish gum of 10 mg per 10 cc. and an induction period of '10hours. The anti-knock rating roseli from 6'1 to '70 octane.

Example .3.An unrefined cracked gasoline was pumped through my catalyticmass at a temperature between 200-300 C. and a pressure sufficient tosubstantially maintain the liquid 0' state. Oleflns containing gas suchas is obtained in cracking were added to the hot gasoline in quantitiesso as to form a mixture of gas and liquid. The product obtained wasredistilled to the desirable endpoint and yielded more gasoline 6 thanin a process without using cracked gases. The gasoline obtained wascompletely refined and with a higher octane number than" in a processwithout using cracked gases. The oleflns were apparently polymerizedaromatics.

Example 4.--Benzene was pumped throughmy catalytic masswhile ethylenewas forced, through it at a pressure of 450 pounds per square inch, in

countercurrent to the benzene. A temperature I] and condensed with so of250 C. was maintained in the reaction chamfrom the group consisting ofsulfuric acid and her. The resultant liquid was fractionated for sludgeacid, calcined at a temperature suilicient separating ethyl benzene fromthe unreacted bento largely expel the tree sulfuric acid but below zene.Ethylization was 60% complete. red heat. I

6 Example 5.-Ethy1ene at the initial pressure of 3. A process for thepolymerization of a mix- I 700 pounds per square inch was heated in anture oi oleflnic and paramnic gases, consisting in autoclave for eighthours at 340 C. with my heating said mixture in presence of a catalystcatalyst. About 20% of the ethylene was polyrepresenting a product oi' amixture of a sub-' merized by this method into gasoline. The stancetaken from the group consisting of a min- 10 higher boiling constituentsof the polymer coneral phosphate, superphosphate, and Thomas 10 tainedkerosene, Diesel oil, and lubricating oils. slag, with a'substance takenfrom the group I claim as my invention: consisting of suli'uric acid andsludge acid.

1. A process for the polymerization of gaseous calcined 'at atemperature below red heat until products resulting from a hydrocarbonoil cra'ckthe free sulfuric acid is largely expelled, the heatingprocess, comprising subjecting the gaseous ing of the gaseous mixturebeing conducted at 1 products to the action or a catalyst consisting ofthe temperature from about 100 to 450 C. until a product of a mixture ofa substance taken from the parafllnic gases are converted into oleflnicthe group consisting 01' a mineral phosphate. gases, and polymerizingthe oleflnic gases in superphosphate; and Thomas slag, with asubpresence or said catalyst at such temperature and U stance taken fromthe group consisting of sulfuric pressure conditions as to polymerizethe gaseous acid and sludge acid, calcined at a temperature productsinto liquid hydrocarbons. sufllcient to largely expel" the free sulfuricacid 4. A step in the process of polymerization of a but below red heat,the treatment being conmixture oi. oleflnic and paramnic gases obtainedducted at such pressure and temperature condiduring cracking process ofpetroleum oils, con- 26 tions as to polymerize the gaseous product intosisting in converting parafllnic gases into oleflnic l5 liquidhydrocarbons. gases by heating the mixture of said gases- 2. A pr c sfor th p lym i ation of gaseous at a temperature of about 400 to 450 .0.in products resulting from a hydrocarbon oil crackpresence of a catalystcomprising a product of a ing process, comprising subjecting the gaseousmixture of a substance taken from the group con- 80 products at atemperature from 200 to 250 C. .sis'ting of a mineral-phosphate,superphosphate, I)

' and at a pressure of 7 to 15 atmospheres to the and 'Thomasslag, witha substance taken from action of a catalyst consisting of a product of athe group consisting of sulfuric acid and sludge mixture of a substancetaken from the group acid, calcined at a temperature below red heatconsisting of a mineral phosphate, superph0suntil the" free sulfuricacid is largely expelled.

85 phate, and Thomas slag with a substance taken BORIS MALIBHEV. 85 t

